Process for breaking petroleum emulsions, certain oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins and method of making same



was

PROCESS FoR BREAKING PnrnoLnUM EMUL- SIONS, CERTAIN OXYALKYLATED'POLYEPOX- IDE-TREATED" AMlNE-MQDIFIED THERMO- P ASTIC HENQ AL HYDE R SINS AND ETHO QF MA NG Melvin De Groote, University City, and Kwau-Ting Shep, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application July 30, 19.53, Serial No. 371,410

20 Claims. (Cl. 252-344) The present invention is a continuation-in-part of our copending application, Serial No. 364,501, filed June 26, 1 953. 1

Our invention provides an economical and rapid process for resolving petroleum emulsions of the waterin-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulson.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft Waters or weak brines. trolled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipe line oil.

The present invention relates to the breaking of petroleum emulsions by the use of compounds obtained by oxyalkylating with a polyepoxide the products obtained by condensing phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over o'phenolic nuclei per resin molecule, which resins are reaction products of 2,4,6 C4-C24 aliphatic substituted phenols with a C1'Ca aldehyde, with a basic non-.hydroxylated secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and formaldehyde followed by reacting this product with ethylene, propylene, or butylene oxide, glycide or methyl glycide, or mixtures thereof, and with the use oftwo moles of the resin condensate to one mole of the polyepoxide, the polyepoxide being non-aryl, as more fully explained hereafter.

The diepoxides employed in producing the products used in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, SerialNo. 364,501, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalentcompound, such as glycerol or diglycerol, with epichlo'r'ohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. See, for example, Italian Patent No. 400,973, dated August 8, 1951; see, also, British Patent 518,057, dated December 10, 1938; and UPS. Patent No. 2,070,990, dated February 16, 1937 to Gross Con- 2,771,451 retes e rt .1956

2 et al. Reference is made also to U. S. Patent 2,581,464, dated lanuaryb, 1952 to Zech. This particularlast mentioned patent describes a composition of the followng i'sei e al ffimul O I increases],

in which x is at least 1, z varies from less than 1 to more than 1, and x and 2 together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above formula, and any remaining groups of the residue being :free hydroxyl groups.

It is obvious from what is said in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl radical; thus, the formula would become Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating'belowthe point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that is sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the solvent selected would have to be one which isnot susceptible to oxyalkylation as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usualy limited'to the 1,2- epoxyring. .The 1,2-epoxy ring is sometimes referred to as the oxir ane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has twojor more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the'standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4epoxybutane(1,2-3,4 diepoxybutane).

It Well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may. be important to note that somewhat similar c'ompounds, generally of much higher molecular weight, have been-described as'complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins.

Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference 'is made to the following formula; 7

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted inthe next to last formula preceding, or low. molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenolaldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in'which n is a small whole number less than 10, and usually less than 4, and including 0, and R1 represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic-acid,

hydroxyacetic acid, gluconic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in the instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are;

distinctly .dispersible in 5% gluconic acid. For instance, the products freed from 7 any solvent can be shakenwith 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products be-. fore and after treatment with a polyepoxide reveals that the polyepoxide by and large introduces increased hydrophile character or, inversely, causes a decreasein hydro-. phobe character. However, the solubility characteristics of the final product, i. e., the product obtained by oxyalkylation with a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, or propylene oxide and more especially butylene oxide, introduce pri-. marily' hydrophobe character. A mixture of the various oxides will produce a balancing in solubility character: istics or in the hydrophobe-hydrophile character so as to be about the same as prior to oxyalkylation with the monoepoxide.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form ,of the free base or hydrate, i. e., combination with Water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, datedMarch 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the actetate, may not necessarily be xylenesoluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases or vigorous shaking and surface activi ty makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what'is said hereinafter will be divided into seven parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary amines free from a hydroxylr adi cal which may be employed in the preparation of the herein-described aminernodified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides, and particularly diepoxides;

Part 5 is concerned with reactions involving the two preceding types of materials and examples obtained .by such reaction. Generally speaking, this involves nothing more than reaction between 2 moles of a previouslypliepared amine-modified phenol-aldehyde resin condensate as described and one mole of a hydrophile polyepoxide so as to yield anew and larger resin molecule, or comparable product;

Part 6 is concerned with the use of a monoepoxide in oxyalltylating the products described in Part 5, .preceding, i. e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

'Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 ,Insome instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula The diepoxides previously described may be indicated by the following formula:

H R 1 R H HO-O R" -CCH .ln

in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two termina epoxide groups, and n is the numeral 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide :iR" is CH2.-CH2 and n is 1. l-nanother example previously referred toR is CHaOCHaandn' is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory 'quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which'is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ringradical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula jbecomesz in the above formula R1 is selected from groups such as the following:

. CsHsOCsI -Is CsHeOCsHsOCsHe Cal-Is CaHs OH) OCaHs OH) Cel -1st OH) OCaHs OH) OCsHs OH) It is to be noted that in the above epoxides there is a complete absence of '(a) aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R1 is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol OHROH must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HQROH, in which the oxygen-linked hydrogen atoms were replacedby Thus, R(OH)n where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbonatoms or thereabouts.

Referring to a compound of the type above in the formula having; or more carbon atoms in an uninterrupted chain. This; particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of; epichlorohydrin yield one mole of the diglycidyl ether, or, statedanother way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular Weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide wilLbereferred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may by hydroxylated or represent a ,heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxy groups into epoxy radicals.

See also Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula R R R In the above formula n represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei 'varies from 3 to 6, i. e., n varies from 1 to 4; R respresents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as butyl, 'amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehydeit may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

2 1 Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. 'Thisris particularly true where the resins are derived from trifnnctional phenols as previously noted. However, .even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example of U. S. Patent No. 2,449,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No.- 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R R R The'basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a ,very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

0 H i" O H "I 0 H RIII R!!!- .R R nR in which R'" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasome which areebvieus the condensation pro-duo: attain-en appear 2 to be described best in teriiis of the method of manufacture Resins can be made using an acid catalyst or basic cata- I'y'stpr' a catalyst havin neither acid nor basic pro erties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is prefeiable' that the base be neutralized although We have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as 'r'micli as a few lths of a percent. Sometimes moderate increase .in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In. preparing resins one does not get a single polymer, i. e, one having just 3 units, or just 4 units, or just units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight. may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than these whichare lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in thefollowmg table:

TABLE I M01. wt Er- 7 RT of resin ample R Position derived n molecule number 01 R 0m (based on n-l-2) 1a; Phenyl Para F0rma1= 3. 5 992. 5

. e r Tertiary butyl 1 3.5 882.5 Secondary butyl 3. 5 882. 5 Cyc1obexy1 3.5 1, 025.5 Tertiary amyL 3. 5 959. 5 Mixed secondary 3. 5 805. 5 and tertiary amyl. Pronyl .1 3. 5 805. 5 Tertiary hexyl 3. 5 1, 036. 5 Octyl 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 4981 5 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3; 5 1,330.5 Tertiary butyl 3. 5 1, 071.5

Tertiary amyl; i.. o... 3. 5' 1,148.5 Nonylm do 3; 5 l, 456. 5 Tertiary b'utyl. Propion 3. 5 1-, 008. 5

ehyde.

3.5 1, 085. 5 Nony1 3. 5 1,393.5 Tertiary butyL 4; 2 996. 6

Tertiary amyl 4. 2 1, 083,14 Nqnyl 4. 2 1,4305 6 Tertiary butyL 4. 8 1, 094: 4 Tertiary amyL- 4.8 1,189J6 N 1 4. 8 1, 570. 4 1. 5 604. 0 1. 5 646:0 1. 5 653:0 1. 5 688.0

PART 3 Ashas been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine, and preferably a strongly basic secondary monoamine,

i0 freefiom hydrdrryr groups wiiose composition is intimated thus:

in which R represents a monovale'nt alkyl, alic'yclic, n91: alkyl radical and maybe hetefocyclic in a few instances as in the case of piper'idine' and a secondary amine derived from fur-furylamine by methylation orethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as diifiethylaniine, methylethylamine, dieth'ylam'ine, dipropylam'ine, eth ipre 'lamine; dibutyl amine, diamylarnine, dihexylam'ine', dioctylainir'ie, and d i= nonylamine. Other amines include bis'(.l,3-dime't ylbutyl) amine. There are, of course, a variety of primary amines which can be reacted with an alkylatiiig agent siicli as d'ime'thyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc, to produce suitable a'n'iines' within the herein specified limitations. For example, one can methylate' aIphaqfiet'hyl-BenZyIaminE, or benzylamine itself, to roduce a suitable reactant; Needless to say, one can use secondary amines such as dicycloheiiylamine, dibutylafniriie oi" amines'contajinin one cycloheiryl grasp and one alkyl group, oron'e be'nzyl group and one alkyl group, such as" ethylcycloheiryl amine, ethylbenzylamine, etc.

Another class of amines which are particularly desirable for" the reason that they introduce a definite hydrophile effect by virtue of an ether linkage,- or repetitious ether linkage, are certain basic polyester amines orthe formula [R'(O Cn Zn 21m NH q in which x is a small whole number having a value of 1 or more, and may be as much as 10 or 12'; n is an integer having ava lue of 2 to 4, inclusive; m represents the numer'al 1 to 2; and rri' represents a number 0 to 1, with the proviso that the sum of m plus m equals 2; and R has its' prior significance. particularly as a hydrocarbon radical.

Examples of such compounds are:

Other somewhat similar secondary amines are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et-al. In the above formula R may be" methyl, ethyl, propyl, amyl, octyl, etc;

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by PART 4 The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to .a .singlephase system, and since temperatures up to 150 C.'or thereabouts may be employed, it is obvious that the proceduce becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the fol lowing details are included.

A convenient. piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In'most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is'apt to be a solid at ordinary or higher temperatures, for instance, ordinary room. temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water. is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down tov about 30% formaldehyde. However, paraformaldehyde can be used but it is more diflicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. vents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this, (0) is an efiort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted low molal soluble amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is not objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low.

temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason.

In heating and stirring the reaction mass there is a ten dency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss.- Here, again, this lower temperature is not necessary byvirtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants.

and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances.

On the other hand, if the products are not mutually.

soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the However, if the resin is prepared as such it may be added Petroleum solvents, aromatic sol Everything else being equal, wev

particular advantage in this.

were;

a N 13. in solution form, just as preparation is described .in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least thereaction temperature orsomewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out We prefer to use a solution and whether to use a commercial 37% concentration is simply a matterof choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difiiculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove Water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difiiculties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed. Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature; for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phase separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C.,and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The. removal of the solvents is conducted in a conventionalmanner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of, reactants goes we have invariably employed approximately one mole of the resin based on the molecular Weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage'in this. In other cases we have used a slight excess of amine several hours.

r 14 21nd, again; have not f1 Ind any particular advantage in so doing. Whenever feasible we have checked the coinplet'eness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity. particularlylin a dilute acetic acid solution. The nitrogen content after removal of unreacted amine; if any is present, is another index. I i l In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

identified previously as Example 2a. lit was obtained from a para-tertiary butylphenol and formaldehyde.

The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corr'esponded to an average of about 3 /2 phenolic nuclei, as

the value for rt which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin 50 obtained in a neutral state had alight amber color. u

882 grams of'the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution wascomplete. It was then adjusted to approximately 30 C. to 35 C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde addedslowly. ,The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At theend of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to-tirne, and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within 2 to 3 hours after refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solutionand reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped.

During this time any additional water, which was'probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. Time can be reduced by cutting low temperature period to approximately 3 to 6 hours.

Note that in Table 11 following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

. Note that as pointed out previously, this procedure is employed was 882 grams. All this has been described illustrated by 24 examples in Table II. prev1ously.

' TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tion, tlon distill. No. used grs. hyde soln. and amt. tem time, temp.,

and amt. hrs. 0.

882 Dlethylamlne, 146 grams 37%, 162 g.-. Xylene, 882 g--- -25 150 480 Diethylamine, 73 grams.-. 37%, 81 g Xylene, 480 g 22-30 24 152 633 d 30 Xylene, 633 g s 21-24 38 147 441 Dlbutylamine, 129 grams 37% Xylene, 441 g. 25-37 32 149 480 Xylene, 480 g 20-24 149 633 do Xylene, 633 gm. 18-23 24 150 882 Morpholine, 174 grams 37%, 162 g... Xylene, 882 g 20-26 35 145 480 Morpholine, 87 grams. 37%, 81 g. Xylene, 480 g- 19-27 24 156 633 do .do Xylene, 633 g.-. 20-23 24 147 473 Dioctylamine (di-2-ethylhexylamine), 117 grams 30%, 100 g... Xylene, 473 g.-. 20-21 38 148 511 do .do Xylene, 511 g 19-20 30 145 665 do 37%, 81 g" 20-26 24 150 441 (C1H O C2H4OO2H4)NH, 250 grams. 30%, 100 g 20-22 31 147 595 (G1H5OC H4OC H02NH, 250 grams. 37%, 81 g Xylene, 595 g--. 23-28 25 145 441 (04H9OGH2OH(CH3)O(CH3)CHOH2)2NH, 361 grams do Xylene, 441 g.-. 21-23 24 151 480 ((hHnOCHzCHOHs)OECHQGHCHQMNH, 361 grams 24 150 511 (0 11 001120151 OHQO CH3)CHOH2)2NH, 361 grams 25 146 498 EOHzOOHiOHzOCHgOHOGHiOHQzNH, 309 grams... 24 140 542 CH3OCH2CH2OOH2CH2OCH2OH2)2NH, 309 grams. 30 142 547 (CHsOCHzCHgOCHzCHzOCHzOH2)zNH, 309 grams. 26 148 441 (CHSOCH2OH2OH2CH2OH2CH2)2NH, 245 grams 28 143 595 ECHIOCH2CHICH2GHZCH2OHZ 2NH, 245 grams. 25 146 391 OHIlOCH2CH2CHZOH2CH2OH2)2NH, 98 grams 30% 50 24 145 PART 5 Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and the amine condensate and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactants, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employedwould be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solventfree and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve.

Example 10 employed was 162 grams, and the amount of solvent The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of a diepoxide.

In any event, grams of the condensate dissolved in 105 grams of xylene were stirred and heatedto 106 C., 18.5 grams of the diepoxide previously identified as A and dissolved inan equal weight of xylene were added dropwise. The initial addition of the xylene solution carried the temperature to about 108 C. The remainder of diepoxide was added during approximately an hour's time. During this period of time the reflux temperature rose to about C. The product was allowed to reflux at a temperature of about C. using a phaseseparating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about a maximum of C. The mixture was refluxed at 185 C. for approximately 3 hours. Experience has indicated that this period of time was sufficient to complete the reaction. At the end of the period the xylene which had been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in order to examine the physical properties. The material was a dark red viscous semisolid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without thefurther addition of a little acetone. 7

The procedure employed of course is simplein light of what has been said previously and in efiect is a procedure similar to that employed in the use-of .glycide or methylglycide as oxyalkylating agents. See, for example, Part 1 of U. S.-Patent No. 2,602,062dated July 1, 1952, to De Groote.

17 Various examples obtained in substantially the same manner are enumerated in the following tables:

theoretical amount of diepoxide, for instance 90% or 95% instead of 100%. The reason for this fact may TABLE III Con- Time Ex. den- Amt, Diep- Amt, Xylene, Molar of new Max. No. sate grs. oxide grs. grs. ratio tion, temp., Color and physical state used used hrs. 0.

105 A 18.5 123. 5 2:1 4 185 Brown viscous semi-solid. 124 A 18. 5 142. 5 2 :1 4 180 D0. 108 A 18.5 126. 5 2:1 4 188 Do 116 A 18.5 134. 5 2:1 1 178 Do 120 A 18.5 138. 5 2 :1 4 190 Do. 159 A 18.5 177. 5 2:1 4. 5 185 Do. 141 A 18.5 159. 5 2:1 4. 5 182 D0. 177 A 18.5 195. 5 2:1 4. 5 188 D 164 A 18.5 182. 2:1 4. 5 180 Do 173 A 18. 5 191. 5 2:1 4. 5 192 Do.

TABLE IV Con- Time Ex. den- Amt., Diep- Amt, Xylene, Molar of reae- Max. No. sate grs. oxide grs. grs. ratio tion, temp, Color and physical state used used hrs. 0.

105 B 11 116 2:1 4 175 Brown viscous semi-solid. 124 B 11 135 2:1 4 175 Do. 108 B 11 119 2:1 4 180 Do 116 B 11 127 2:1 4 182 Do. 120 B 11 131 2:1 4 178 Do 159 B 11 170 2:1 4 182 Do. 141 B 11 152 2:1 4 185 D0. 177 B 11 188 2:1 4 178 Do. 164 B 11 175 2:1 4 183 Do. 173 B 11 184 2:1 4 180 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE V Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule TABLE VI Probable Probable Resin conmol. wt. of Amt. of Amt. of number of No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule At times We have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of dlepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another pro cedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also,.we have found it desirable at times to use slightly less than apparently the reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular Weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CHz (Resin) CH2(Amine) Following such simplification the reaction product With apolyepoxide and particularly a diepoxide, would be indicated thus:

[(Arnine) CH2(Resin) CHz(Amine)] /D.G.E.

[(Amine) CHc(Resin) CH (Amine)] in which D. G. E. represents a diglycidlyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) OH (Amine)]\ /D.G.E. [(Amine) CH (Amine)] [(Resin) OHr(Resin)] D.G.E [(Resin) CH2(RGS1I1)] [(Amine) OHz(Amine)] /D.G.E. [(I-lesin)] All the above indicates the complexity of the reaction product obtained after treating the aminemodified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part 5, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves theuse of a monoepoxide or the equivalent. The principal difference is only that while I polyepoxidesare invariably nonvolatile and can be re actedunder a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. purpose of convenience, it is most desirable to conduct the previous reaction, i.e., the one involving the polyepoxide,

in equipment such that subsequent reaction with mono epoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may represent less of' a hazard than glycide, yet these reactants should be handled with extreme care. 1 One suitable procedure involves the use of propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed, hydrophile character can be reduced or balanced by use of some other oxide, such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner. See article entitled Ethylene oxide hazards and methods of handling, Industrial and Engineering Chemistry, volume 42, No. 6, June 1950, pp. 1251-l258. Other procedures can be employed as,

, for example, that described in U. S. Patent No. 2,586,767,

dated February 19, 1952, to Wilson.

The amount of monoepoxides employed may be as high as,50 parts of monoepoxide for one part of monoepoxide treated amine-modified phenol-aldehyde condensation product.

Example ID The polyepoxide-derived oxyalkylation-susceptible compound is the one previously desiginated as 10. Polyepoxide-derived condensate 1c was obtained, in turn, from condensate 2b and diepoxide A. Reference to Table II shows the composition :of condensate 212. Table II shows it was obtained from resin 5a, diethylamine and formaldehyde. Table I shows that resin 5a was obtained from tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylanon-susceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may'have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated, as stated, on a solvent-free basis.

12.35 pounds of the polyepoxide-derived condensate were mixed with 12.40 pounds of solvent (xylene in this series), along with one pound of finely powdered caustic sodas as a catalyst. The reaction mixture was treated with 6.25 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 28.5 to one, and the theoretical molecular weight was approximately 3700.

Adjustment was made in the autoclave to operate at a temperature of about 125 C. to 130 C., :and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the oxide in Actually, for

approximately-30 minutes and then continue stirring for a half-hour longer, simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide probably could have been injected in 15 minutes instead of a half-hour and the subsequent time all-owed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making sometests on various oil field emulsions.

The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables VII, VIII and IX.

The size of the autoclave employed was 35 gallons. In innumerable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylaticn on :a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 21) This simply illustrates further oxyalkylation iof Example 1D, preceding. The oxyalkylation-susceptible compound 1c is the same as the one used in Example 1D, preceding, because it is merely a continuation. In subsequent tables, such as Table VII, the oxyalkylatio-n-susceptible compound in the horizontal line concerned with Example 2D refers to oxyalky'lation-susceptible compound 10. Actually, one could refer just as properly to Example ID at this stage. It is immaterial which designation is used so long as it is understood such practice is used consistently throughout the tables. In any event, the amount of ethylene oxide introduced was the same as before, to wit, 6.25 pounds. This meant the amount of oxide at the end of the stage was 12.50 pounds, and the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 37 to 1. The theoretical molecular weight was approximately 5000. There was no added solvent. In other words, it remained the same, that is, 12.40 pounds and there was no added catalyst. The entire procedure was substantially the same as in Example 1D, preceding.

In this, and in all succeeding examples, the time and pressure were the same as previously, to wit, to C., and the pressure 10 to 15 pounds. The time element was only one-half hour because considerably less oxide was added.

Example 3D The oxyalkylation proceeded in the same manner as in Examples 1D and 2D. There was no added solvent and no added catalyst. The amount of oxide added was 6.25 pounds. The total amount of oxide at the end of the stage was 18.75 pounds. The molal ratio of oxide to condensate was 85 to 1. The theoretical molecular weight was approximately 6200, and the time period was 45 minutes with temperature and pressure being the same as in preceding Example 2D.

Example 4D The :oxyalkylation was continued and the amount of oxide added was the same as before, to wit, 6.25 pounds. The amount of oxide added at the end of the reaction was 25.0 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was the same as before. The reaction at this point showed modest, if any, tendency to slow up. The molalratio of oxide to oxyalkylation- 2i susceptible compound was 1 113.6 to 1,. The theoretical olecu r weight was about .7500.

Example 5D The oxyalkylation was continued with the introduction of another 6.25 pounds of oxide. No added solvent was introduced and likewise no added .catalyst was introduced, The theoretical molecular weight at the end of the reaction was approximately 8700. The molal ratio of oxide to oxyalkylation-susceptible compound was 142.0 to 1. The time period was increased to one hour.

Example 6D The same procedurewas followed as in the previous examples, without the addition of either more catalyst or more solvent. The amount of oxide added was larger than before, to wit, 18.75 pounds, The amount of oxide at the end of the reaction was 50.0 pounds. The time required to complete the reaction was slightly more than previously, to wit, 1% hours. At the end of the reaction period the ratio .of oxide to oxyalkylation-susceptible compound was 227 to l, and the theoretical molecular weight was 12,500.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables VII through XII.

In substantially every case a 35-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a l5-gallon autoclave and then transferred to a 25-gallon autoclave, or at times to the 35-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring to Tables VII, VIII and IX, it will be noted that compounds 1D through 18D were obtained by the use of ethylene oxide, whereas Examples 19D through 36D were obtained by the use of propylene oxide; and Examples 37]) through 54D were obtained by the use of butylene oxide.

Referring now to Table VIII specifically, it will be noted that the series of examples beginning with 1E were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 2D as the oxyalkylation-susceptible compound. This applies to series 1E through 18E.

Similarly, series 1913 through 36E involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19E was prepared from 24D, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 37E through 54E involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55E through 72E, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73E through 90E involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1F through 18F the three oxides were used. It will be noted in Example IF the initial compound was 78E; Example 78E, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1F through 6F was by use of ethylene oxide as indicated in Table IX.

Referring to Table IX, in regard to Example 19F it will be noted again that thethree oxides were used and 19F was obtained from 60E. Example 60E, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19? and subsequent examples, such as 20F, 21F, etc., propylene oxide was added.

Tables X, XI and XII give the data in regard to the 22 yalkylati n pro re s far as t mp ratur and P sure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table VII in greater detail, the data are as follows: The first column gives the example numbers, such as 1D, 2D, 3D, etc. etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1D through 6D, is Example 1C, although it would be just as proper to say that in the case of 2D the oxyalkylation-susceptible compound was 1D, and in the case of 3D the oxyalkylationsusceptible compound was 2D. Actually, reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the epoxidederived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular oxyethylation step. In the case of Example 1D there is no oxide used but it appears, of course, in 2D, 3D, and4D, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is in+ variably powdered caustic soda.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the oxyalkylation-susceptible compound which in this series is the polyepoxide-den'ved condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide and column twelve shows data for butylene oxide. For obvious reasons these can be ignored in the series 1D through 181).

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the solvent at the end of the oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxide to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table VII, to wit, Examples 19D through 36D, the situation is the same except that it is obvious that the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table VII, Examples 11) through 18]), now carries data as to the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37D through 54D in Table VII, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixderived condensate 1c.

23 ti-on step. Column twelvegives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylationsusceptible compound.

Table VIII is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data do not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1E, in turn, refers to 5D, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide go back to the original diepoxide- This is obvious, of course, because the figures 142.0 and 42.6 coincide with the figures for 5D derived from 1C as shown in Table VII.

In Table VIII (Examples 19E through 36E) the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples suchas 37B and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and

- 24 the table makes it plain that ethylene oxide was used first. Inversely, Example 55B and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73E and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with IE, Table IX, particularly 2F, 3F, etc., show the use of all three oxides so there are no blanks as in the first step of each stage where one oxide is missing. It is not believed any further explanation need be offered in regard to Table IX.

As previously pointed out certain initial runs using one oxide only, or in some instances .two oxides, had to be duplicated when used subsequently 'for further reaction. It would be confusing to refer to too much detail in these various tables for the reason that all the data appear in considerable detail and is such that all results can be readily shown.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables X, XI and XII give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1D through 6D.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the TABLE VII Composition before Composition at end Oxides Oxides Molal ratio Ex. No. 080, Oata- Sol- 080, Cata- Sol- Theo.-

ex. 080, lyst, vent, lbs. lyst, vent, ggf gg f a f mol. No. lbs. EtO, PrO, B110, lbs. lbs. EtO, PrO, BuO, lbs. lbs. alkyl alkyL 81kg] wt.

lbs. lbs. lbs. lbs. lbs. lbs. susceph suscept Suscept cmpd. cmpd cmpd.

1D 1c 12.35 1.0 12.40 12.35 6. 25 1.0 12.40 28.4 3,720 2D 1c 12. 35 6. 25 1. 12.40 12.35 12.50 1. O 12.40 56. 8 4, 970 3D 1c '12. 35 12. 50 1. 0 12.40 12. 35 18. 75 1. 0 12.40 85. 2 6, 220 4D 1c 12. 35 18. 75 1. 0 12.40 12.35 25.0 1. 0 12.40 113. 6 7, 470 5D 12.35 25.0 1. 0 12.40 12.35 31. 25 1. 0 12. 40 142.0 8, 720 6D 1c 12.35 31. 25 1. 0 12.40 12.35 50.0 1. 0 12. 40 227. 2 12, 470 7D 2c 14. 25 1. 0 14.20 14.25 7. 0 1. 0 14.20 31.8 250 8D 26. 14.25 7. 0 1. 0 14.20 14.25 14.0 1. 0 14.20 63. 6 5, 650 9D 2c 14. 25 14. 0 1. 0 14. 14. 21.0 1. 0 14. 20 95. 4 7, 050 10D 2c 14. 25 21. 0 1. 0 14.20 14. 25 28. 0 1. 0 14. 20 127. 2 8. 450 2c 14. 25 28. 0 1. 0 14. 20 14. 25 42.0 1. 0 14. 20 190. 8 11, 250 2c 14. 25 42. 0 1. 0 14. 20 14.25 56. 0 1. 0 14. 20 254. 4 14, 050 3c 12. 65 1. 0 12.70 12.65 4. 25 1. 0 12.70 19.3 3. 380 3c 12. 65 4. 25 1. 0 12. 70 12.65 8. 5O 1. 0 12.70 38. 6 4. 230 3c 12. 65 8. 50 1. 0 12. 70 12.65 12. 75 1. 0 12. 70 57. 9 5, 080 12.65 12.75 1. 0 12.70 12.65 17.0 1. 0 12.70 77. 2 5, 930 12. 65 17.0 1. 0 12.70 12.65 25. 5 1. 0 12.70 115. 8 7, 630 12.65 25. 5 1. O 12.70 12.65 51.0 1. 0 12. 70 231. 6 12, 730 12. 1. 5 12.4 12.35 1. 5 12. 4 2. 6 4, 940 12.35 1. 5 12.4 12.35 24. 70 1. 5 12.4 85. 2 7, 410 12. 35 1. 5 12. 4 12. 35 37.05 1. 5 12.4 127. 8 9, 880 12. 35 1. 5 12.4 12. 35 49. 4 1.5 12. 4 170. 4 12, 350 12.35 1. 5 12.4 12. 35 61. 75 1. 5 12.4 213. 0 14, 820 12.35 1. 5 12.4 12.35 74.10 1. 5 12.4 255. 6 17, 290 14.25 1. 5 14.2 14.25 14.25 1, 5 14. 2 49. 2 5, 700 14.25 1. 5 14. 2 14.25 28. 1.5 14. 2 98. 4 8, 550 14.25 1. 5 14.2 14. 25 42. 75 1. 5 14.2 147. 6 11, 400 14. 25 1. 5 14. 2 14. 25 57. 0 1. 5 14. 2 196. 8 14, 250 14.25 1. 5 14. 2 14.25 71. 25 1.5 14.2 246.0 17, 100 14.25 1. 5 14. 2 14.25 85. 5 1. 5 14. 2 294. 2 19, 950 12.65 1. 5 12.7 12.65 12.65 1.5 12.7 43. 6 5, 060 12.65 1. 5 12.7 12.65 25. 30 1. 5 12.7 87. 2 7, 590 12. 65 1. 5 12.7 12.65 37. 95 1. 5 12. 7 130. 8 10, 120 12.65 1.5 12. 7 12.85 50. 1. 5 12.7 174. 4 12, 650 12.65 1. 5 12.7 12.65 1. 5 12.7 261. 6 17, 710 12. 1. 5 12.7 12. 65 1. 5 12. 7 348. 8 22, 770 12. 35 1. 0 12.4 12.35 12. 35 1. 0 12.4 34. 3 4, 940 12. 35 12. 35 1. 0 12. 4 12. 35 17. 29 1. 0 12. 4 48. 02 5, 928 12. 35 17. 29 1. 0 12. 4 12.35 22. 23 1. 0 12. 4 61. 74 6, 916 12. 35 22. 23 1. 0 12. 4 12.35 27. 17 1. 0 12. 4 75. 46 7, 904 12. 35 27. 17 1. 0 12. 4 12.35 32. 11 1. 0 12. 4- 89. 18 8, 892 12. 35 32.11 1. 0 12.4 12.35 37.05 1. 0 12. 4 112. 9 9. 880 14.25 1. 0 14.2 14. 25 14.25 1. 0 I 14. 2 39. 6 5, 700 14. 25 14. 25 1. 0 l4. 2 14. 25 19. 95 1. 0 14. 2 55. 44 6, 840 14; 25 19.95 1. 0 14.2 14.25 25. 65 1. 0 14.2 71. 28 7, 980 14. 25 25. 65 1. 0 14. 2 14. 25 31. 35 1.0 14. 2 87. 12 9, 120 14. 25 31. 35 1. 0 14. 2 14. 25 37. 05 1. 0 l4. 2 102. 96 10, 260 14.25 37.05 1. 0 14.2 14.25 42. 75 1. 0 14.2 118. 11, 400 12. 65 1. 0 12. 7 12. 65 12. 65 1. 0 12.7 35. 1 5, 060 12. 65 12. 65 1. 0 12. 7 12. 65 17. 71 1. 0 12. 7 49. 14 6, 072 12.65 17.71 1. 0 12. 7 12.65 22.78 1. 0 12. 7 63. 18 7, 084 12. 65 22. 78 1. 0 12.7 12. 65 27. 84 1. 0 12. 7 77. 22 8, 096 12. 65 27.84 1. 0 l2. 7 12. 65 32. 9 1. 0 12. 7 91. 26 9, 108 12. 65 32. 9 1. 0 12. 7 12. 65 37. 96 1. 0 12. 7 105. 3 10,

Theo. mol. wt.

OO OOO OOOOOOOUUOOOOO000000000000000864200 00000243080000 000000000. 642 63 740 050569258194.9494555555272777421 94. M8 60678902 000 @161 161605532097273839257025963048643189999%83N23H68111122% h%%w oHm852%m9865 9m nnw onwl 3 cq1w4 7 w2 7 0 2'&7 1 1 2 72 5 6 7 v 1 y 1 y r 1 11122 11112223333mmm22 11 flu M NHHHHNH oxyalkyl.

cmpd.

oxyalikyl.

pt. suscept. cmpd.

628406246802628468666 666888888888 2 5 7 oinlommmnmidiifiymfififiamononfim Molal ratio EtO to PrO to BuO to oxyaikyl. suscept. susce cmpd.

Solvent, lbs.

2222224 4 2 i 2 22244444422 2 2 2 4444422221222 222444444 22222 1111111mmmlmlmmmmmmmmmmmummmmnHUBmmmmmmlllllllllllwlmmlmlmmmm l1111111211 1 11111 111 11111 Catalyst, lbs.

Composition at end Oxides PrO, B110,

may remove traces or small amounts of uncombiin ed oxide, if present and volatile under the conditions employed.

555555 5 5 5 5 5 505 2222220000000000O022m- 0%m050005@70500000000000005555552257025050 0025705 TABLE VIII oso, S.

2 2 2 2 2222 2 2244444422 22 2 4 442 22222222224 1m1m1nMMMMMm1mmmummmmmummmnmmmmmuilllm ml lli1111lmmmuullmlmnniu l mi l i ion, an

S01- vent,

lbs.

Catalyst, lbs.

Such distillation also lbs.

32211 29630 G778mw00OO0077777999999111111999999666666 7 2 7 2 4 9 5 1 7 22 7 7 2 7 7 7 7 2 2 2 2 2 7. 7 -l 7 7 9 9 0m 9 0m2 2 2 2 Oxides 1 1 1 U 5 5 5 5 505 %%2%%% n w 2%z o WO .WOEUO 72%7050000000000005555 5 2570 0 05 5 5 Composition before m0, Pro, 13110,

- .444444111111.. .1 t a I t a 275000000 555555 6 5 275 mmmmmm mg "E mnm l iizsgssseg ozzzzzz 7 mm... n mnu 112 080, lbs.

ex. No.

Ex. No.

solvents as indicated by the figures in the tables. If desired, she solvent may be removed by distillat particularly vacuum distillation.

TABLE IX Composition before Composition at and E Oxides Oxides Molal ratw No. 080, Oata- Sol- Cata- Sol- Theo.

ex. 080, lyst, vent, S0, lYSt, vent, Lggf 52 1 mol. No. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. 5,, aIkYI i wt.

I Y 1 lbs lbs. lbs. lbs lbs. lbs suscept Susmmh suscept cmpd. cmpd cmpd.

12.35 27.17 1.5 12.4 12.35 6.25 74.1 27.17 1.5 12.4 28.4 255.6 75. 46 23,974 12.35 6.25 27.17 1.5 12.4 12.35 12.50 74.1 27.17 1.5 12.4 56.8 255.6 75.46 25,224 12.35 12.50 27.17 1.5 12.4 12.35 18.75 74.1 27.17 1.5 12.4 85.2 255.6 75.46 26,474 12.35 18.75 27.17 1.5 12.4 12.35 25.0 74.1 27.17 1.5 12.4 113.6 255.6 75.46 27,724 12.35 25.0 27.17 1.5 12.4 12.35 31. 74.1 27.17 1.5 12.4 142.0 255.6 75.46 28,974 12.35. 31.25.. 27.11 1.5. 12.4 12.35 37.50 74.1 21.17 1.5 12.4 170.4 255.6 75.46 30,224 14.25 19.95 1.5 14.2 14.25 3.50 71.25 19.95 1.5 14.2 '15.9 246.0 55.44" 21, 760 14. 25 3.5 19.95 1.5 14.2 14.25 7.0 71.25 19.95 1.5 14.2 31.8 246.0 55. 44 22,490 14.25 7.0 19.95 1.5 14.2 14.25 14.0 71.25 19.95 1.5 14.2 Y 63.6 246.0 55.44 23,890 14.25 14.0 19.95 1.5 14.2 14.25 21.0 71.25 19.95 1.5 14.2 95.4 246.0 55.44 25.290 14.25 21.0 19.95 1.5 14.2 14.25 28.0 71.25 19.95 1.5 14.2 127.2 246.0 55.44 26,690 14. 25 28.0 19. 95 1.5 14.2 14. 25 42.0 71.25 19.95 1.5 14.2 190.8 246.0 55.44 29,490 12.65 12. 1.5 12.7 12. 65 4.25 75.9 12.65 1.5 12.7 19.3 261.6 35.1 21.090 12.65 4.25 12.65 1.5 12.7 12.65 3.50 75.9 12.65 1.5 12.7 38.6 261.6 35.1 21,940 12.65 8.50 12.65 1.5 12.7 12.65 12.75 75.9 12.65 1.5 12.7 57.9' 261.6 35.1 22,790 12. 65 12.75 12.65 1.5 12.7 12.65 17.0 75.9 12.65 1.5 12.7 77.2 261.6 35.1 23,640 12. 65 17.0 12. 65 1.5 12.7 12. 65 25.5 75.9 '12. 65 1.5 12.7 115.8 261.6 35.1 25,340 12.65 25.5 12.65 1.5 12.7 12.65 34.0 75.9 12.65 1.5 12.7 154.4 261.6 35.1 27,040 12.35 31.25 37.05 1.5 12.4 12.35 31.25 12.35 37.05 1.5 12.4 142.0 42.6 112.9 ,600 12.35 31. 25 37.05 1.5 12.4 12.35 31.25 24.70 37.05 1.5 12.4 142.0 85. 112.9 21,070 12.35 31.25 37.05 1.5 12.4 12.35 31.25 37.05 37.05 1.5 12.4 142.0 127.8 112.9 23,540 12.35 31.25 37.05 1.5 12.4 12.35 31.25 42.05 37.05 1.5 12.4 142.0 145.0 112.9 24,540 12.35 31.25 37.05 1.5 12.4 12.35 I 31.25 47.05 37.05 1.5 12.4 142.0 162.2 112.9 25,540 12.35 31.25' 37.05 1.5 12.4 12.35 31.25 52.05 37.05. 1.5 12.4 142.0 179.4 112.9 26, 540 14.25 21.0 42. 1.5 14.2 14. 25 21.0 14.25 42.75 1.5 14.2 95.4 49.2 118.8 18,450 14.25 21.0 14. 25 42.75 1.5 14.2 14.25 21.0 28.50 42.75 1.5 14.2 95.4 98.4 118.8 21,500 14.25 21.0 28.50 42.75 1.5 14.2 14.25 21.0 34.2 42.75 1.5 14.2 95.4 118. 08 118.8 22, 640 14.25 21.0 34.2 42.75 1.5 14.2 14.25 21.0 39.9 42.75 1.5 14.2 95.4 137.76 118.8 23, 780 14.25 21.0 39.9 42. 75 1.5 14.2 14. 25 21.0 45.6-v 42.75 1.5 14.2 95.4 157.44 118.8 24, 920 14.25 21.0 45.6 42.75 1.5 14.2 14. 25 21.0 51.3 42. 75 1.5 14.2 95.4 177.12 118.8 26,060 12. 65 29.75 32.9 1.5 12.7 12. 65 29.75 12. 65. 32.9 1.5 12.7 135.1 43.6 105.3 17,810 12.65 29.75 12.65 32.9 1.5 12.7 12. 65 29. 75 25.30 32.9 1.5 12.7 135.1 87.2 105.3 20,340 12. 65 29. 75 25.30 32.9 1.5 12.7 12.65 29. 75 30.36 32.9 1.5 12.7 135.1 104.64 105.3 21,352 12.65 29.75 30.36 32.9 1.5 12.7 12. 65 29.75 35.42 32.9 1.5 12.7 135.1 122.08 105.3 22,364 12. 65 29.75 35.42 32.9 1.5 12.7 12.65 29.75 40.48 32.9 1.5 12.7 135.1 139.52 105.3 23, 376 12.65 29.75 40.48 32.9 1.5 12.7 12.65 29.75 45.54 32.9 1.5 12.7 135.1 156.96 105.3 24, 388

TABLE X :Max. Max. Tm Solublllty em pres., e,

p. s. 1. hrs.

Water Xylene Kerosene -130 10-15 45 Insoluble Insoluble.

125-130 10-15 Emulsiflable. Do.

125-130 10-15 d0 Do.

125-130 10-15 Dispersible.

125-130 10-15 Soluble.

125-130 10-15 Insoluble.

125-130 10-15 Soluble.

125-130 10-15 Insoluble.

5-130 10-15 Slouble.

-150 10-15 Insolbule.

145-150 10-15 Dlsperslble 145-150 10-15 Soluble.

145-150 10-15 Insoluble.

145-150 10-15 Soluble.

145-150 10-15 Insoluble.

145-150 10-15 Soluble.

v v M 29 Obviously, in the useof ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., not attempt to selectively add one and then the other, or any other variant.

TABLE XI Ex. No.

Max. pres., p. s. i.

Solubility Time, hrs.

Water Kerosene lllllllllXilllllllllllllllllllllllll Insoluble.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber, or a straw color, or even a pale straw color. The reason is primarily that no efiort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product; Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difiicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

in column 15 and ending in column 18, reference should be to Example 1E, herein described.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

, l. A process for breakingpetroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said deinulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylatecl secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being TABLE XII Max. Max. Solubility Ex. No. temp., pres, Time,

C. p. s. i. hrs.

Water Xylene Kerosene 10-15 Soluble. l015 Do. 10-15 D0. 10-15 Insoluble 10-15 D0. 10-15 D0. 10-15 Soluble. 10-15 D0. 10-15 D0. 10-15 Insoluble 10-15 D0. 10-15 D0. 10-15 Soluble. 10-15 D0. 10-15 Insoluble 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do.

PART 7 Everything that appears therein applies with equal force and efiiect to the instant process, noting only that where conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact reference is made to Example 13b in said text beginning that the precursory polyhydric alcohol, in which an oxy- 33 gen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide-derived product with a monoepoxide; said nionoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a polyepoxide; and 3) oxyalkylation with arnonoepoxide; said firststep being that of (A) condensing (a) an oXyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical H H H oo-orr in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized bythaving' present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylation and oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2moles of the resin condensate .to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxidederived product with a monoepoxide; said monoepoxide being an alpha-betalalkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a diepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydricp'henol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which Ris an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as 'a second step by (B) reacting said resin. condensate with nonaryl hydrophile diepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical H ,H y H g[C-\-'7CH in the diepoxide is Water-soluble; said diepoxides being free from reactivefunctional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylationsusceptible solvent-soluble liquids and low-melting solids; and said reactionbetween (A) and (B) being conducted below pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; saidmonoepoxide being an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

' 4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5. A process for breaking petroleum emulsions of the water in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a diepoxide, and (3) oxyalkylation with a monoepoxide; said first step being that of, (A) condensing (a|) an' oxy-alkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being .difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water, and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation susceptible; followed as a second step by.(B) reacting said resin condensate with a hydroxylated diepoxypolyglycerol having not more than 20, carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting'of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

6. The process of claim wherein the polyglycerol derivative has not over 5 glycerol nuclei.

7. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted.

8. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and flue precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde.

10. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin is not over 5.

11. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting'of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 7 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 8 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

19. The process of claim 9 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

20. The process of claim 10 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are s uflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the tile of this patent UNITED STATES PATENTS 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID FIRST STEP BEING THAT OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REAGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND A ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUNSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 